EP3567656A1

EP3567656A1 - Cathode material, method for preparing the same, cathode and lithium ion battery

Info

Publication number: EP3567656A1
Application number: EP19172930.0A
Authority: EP
Inventors: Pengwei Chen; Meng Wang; Liang Wang
Original assignee: Ningde Amperex Technology Ltd
Current assignee: Ningde Amperex Technology Ltd
Priority date: 2018-05-07
Filing date: 2019-05-07
Publication date: 2019-11-13
Anticipated expiration: 2039-05-07
Also published as: CN110459735B; ES2904330T3; US20190341649A1; US11024872B2; EP3567656B1; CN110459735A

Abstract

The present application provides a cathode material, a method for preparing the same, a cathode and lithium ion battery having the same. The cathode material includes an active component; and a sodium salt dispersed in the active component.

Description

FIELD

The present application relates to the field of batteries, and more particularly to a cathode material, a method for preparing the same, a cathode and lithium ion battery having the same.

BACKGROUND

Lithium-ion battery, as a secondary chemical power source, has been widely used in small digital products such as mobile phones and has been widely recognized and favored, because of its advantages of clean, environment-friendly, high-efficiency, security and high energy density. However, the security of the lithium-ion battery still restricts its further applications to a large extent.
Cathode material has a significant influence on the performance of the lithium ion battery as an important part thereof. Therefore, it is particularly important to optimize and improve the cathode material constantly. Lithium cobaltate, one of the most widely used cathode materials in the lithium ion battery, has been fully studied through decades of development with respect to its structural characteristics and electrochemical performance, and its synthetic process and industrial production have been quite mature. Even more, by virtue of its higher discharge voltage plateau and high energy density, lithium cobaltate has always dominated the cathode material of consumer lithium ion battery. However, lithium cobaltate also has some disadvantages, for example, phase transition and structural collapse will occur at a high voltage, resulting in deterioration of rate capability, and a contact reaction with an electrolyte results in surface damage and gas production, thereby affecting the security of the battery and shortening the service life of the battery.
Therefore, the current technology related to the lithium ion battery still needs to be improved.

SUMMARY

Embodiments of the present application seek to solve at least one of the problems existing in the related art to at least some extent. For this, the present application is to provide a cathode material having advantages of good stability, high security, high specific capacity, stable rate capability, low thickness expansion rate at high-temperature storage, and high cycle capacity retention rate, etc.
For this, according to embodiments of a first aspect of the present application, there is provided a cathode material, the cathode material includes an active component; and a sodium salt dispersed in the active component.
In embodiments of the present application, the cathode material includes an active component phase and a sodium salt phase, and the active component phase and the sodium salt phase are bonded via a chemical bond.
In embodiments of the present application, a transition region where at least the active component phase and the sodium salt phase are doped with each other is present at an interface between the active component phase and the sodium salt phase.
In embodiments of the present application, the active component phase includes a hexagonal layered structure, and the sodium salt phase includes a layered structure.
In embodiments of the present application, based on a total mass of the cathode material, a mass percent of the sodium salt is in a range of 0.1% to 10%.
In embodiments of the present application, the sodium salt has a chemical structure of Na_aM_cO_b, wherein 0<a≤3, 0<b≤7, 0<c≤3, and M includes at least one element selected from the group of Mo, Cr, Ti and V.
In embodiments of the present application, the sodium salt includes at least one selected from the group of Na₂MoO₄, Na₂CrO₄, Na₂Ti₃O₇ and Na₃VO₄.
In embodiments of the present application, the cathode material has an average particle size of 0.1 µm to 20 µm.
In embodiments of the present application, the active component includes at least one selected from the group of lithium cobaltate, lithium nickel cobalt manganite composite oxide and lithium nickel cobalt aluminate composite oxide.
According to embodiments of a second aspect of the present application, a method for preparing a cathode material is provided. The method includes: ball-milling a mixture of a sodium salt precursor and an active component to obtain a cathode material precursor; and sintering the cathode material precursor to obtain the cathode material.
In embodiments of the present application, the sodium salt precursor is obtained by ball-milling a mixture of a sodium source, an M source and a complexing agent, in which the sodium source includes at least one selected from the group of Na₂CO₃, NaOH, NaNO₃, CH₃COONa and Na₃C₆H₅O₇·2H₂O, the M includes at least one element selected from the group of Mo, Cr, Ti and V, the M source includes at least one selected from the group of MoO₃, H₈MoN₂O₄, Mo(NO₃)₃·5H₂O, Cr₂O₃, CrCl₃·6H₂O, H₈CrN₂O₄, TiO₂, TiCl₄, Ti(NO₃)₄, V₂O₅, V₂O₃ and NH₄VO₃, and the complexing agent includes at least one selected from the group of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), ethylenediaminetetraacetic acid (EDTA) and glucose (C₆H₁₂O₆).
In embodiments of the present application, the sintering is performed in an oxygen or air atmosphere at a temperature of 600 °C to 1000 °C.
According to embodiments of a third aspect of the present application, a cathode is provided. The cathode includes the cathode material as described hereinbefore.
According to embodiments of a fourth aspect of the present application, a lithium ion battery is provided. The lithium ion battery includes the cathode material or the cathode as described hereinbefore.
Additional aspects and advantages of embodiments of present application will be given in part in the following descriptions, become apparent in part from the following descriptions, or be learned from the practice of the embodiments of the present application.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other aspects and advantages of embodiments of the present application will become apparent and more readily appreciated from the following descriptions made with reference to the drawing, in which:
Fig. 1 is a XRD diagram of a cathode material according to an embodiment of the present application.

DETAILED DESCRIPTION

In the following, the technical solutions of the present application will be described in detail with reference to examples. It should be appreciated to those skilled in the art that, the examples described below are explanatory, illustrative, and only used to generally understand the present application, and shall not be construed to limit the present application. Examples which do not indicate specific techniques or conditions are carried out in accordance with either the descriptions in literatures in the related art or the product specifications. Reagents or instruments whose manufacturers are not indicated are conventional products, which are commercially available.
The present application is achieved by the present inventors based on the following knowledge and discoveries.
Although lithium cobaltate has a high discharge voltage plateau and high energy density, its thermal stability and electrochemical stability are poor at a high voltage (usually higher than 4.3 V), it is prone to occur phase transition and structural collapse, resulting in deterioration of the rate capability, and a contact reaction with an electrolyte results in surface damage and gas production, thereby affecting the security of a battery and shortening the service life of the battery. In view of the above problems, the inventors have carried out intensive researches and found out that if a sodium salt is added to an active component, a cathode material obtained thereby has a stable particle surface, the addition of the sodium salt can improve structural characteristics of the active component, so that a battery applying such a cathode material can still maintain a good thermal stability and electrochemical stability, achieve a low expansion rate at high-temperature storage and a high cycle capacity retention rate (good cycle performance), keep a good specific capacity, and further improve its security, even at the high voltage.
In embodiments of a first aspect of the present application, there is provided a cathode material, the cathode material includes an active component; and a sodium salt dispersed in the active component. The inventors found that, by dispersing the sodium salt in the active component, structural characteristics of the active component can be improved, synergetic effects of the sodium salt with the active component are exerted, and the particle surface stability and cycle performance of the cathode material are improved, so that a battery applying such a cathode material maintains a good thermal stability and electrochemical stability, achieves a low expansion rate at high-temperature storage to improve the security of the cathode material, and achieve a high cycle capacity retention rate (good cycle performance) to improve the service life of the cathode material, and still keeps a good specific capacity. Moreover, the sodium salt has a better structural stability than that of the active component, and its structural damage degree at the high voltage (usually higher than 4.3 V) is much less than that of the active component, which allows the cathode material to have a better thermal stability and electrochemical stability even at a high voltage working condition, avoiding occurrences of the phase transition and the structural collapse and the deterioration of rate capability, thereby improving the working security and cycle performance of the cathode material.
According to embodiments of the present application, the active component is not specifically restricted, and can be flexibly chosen by those skilled in the art according to practical demands. In embodiments of the present application, the active component includes at least one selected from the group of lithium cobaltate, lithium nickel cobalt manganite composite oxide and lithium nickel cobalt aluminate composite oxide. These active components not only can meet use requirements of the cathode material, but also can better coordinate with the structure of the sodium salt, thereby guaranteeing that the prepared cathode material has a better cycle performance and electrochemical stability, a low expansion rate at high-temperature storage and a good specific capacity.
In embodiments of the present application, the cathode material includes an active component phase and a sodium salt phase, and the active component phase and the sodium salt phase are bonded via a chemical bond, thereby improving chemical stability, thermal stability, electrochemical stability and structural stability of the cathode material.
In embodiments of the present application, a transition region where at least the active component phase and the sodium salt phase are doped with each other is present at an interface between the active component phase and the sodium salt phase.
It usually occurs at the interface between the active component phase and the sodium salt phase that, metal ions of the active component and the sodium salt enter into crystals of the other one to form an inter-substituted structure, i.e., an inter-doped transition region. In the transition region, at least two kinds of deintercalatable metal ions are involved in charge transfer, such that the inter-substituted structures can effectively stabilize a phase interface of the active component. Furthermore, as the electrochemical stability and the thermal stability of the sodium salt are superior to that of the active component, the addition of the sodium salt can improve the thermal stability and the electrochemical stability of the surface of the active component through physical or chemical bond with the active component phase at the phase interface, and reduce direct contact between the active component and an electrolyte in a battery applying this cathode material so as to further improve the security of the battery. Moreover, several communicated ion channels are formed between these two phases, which will reduce an interfacial resistance in ion migration process, optimize the ion diffusion environment and the cycle performance of the cathode material, and also is beneficial to improvement of the interface stability and the overall conductivity of the material.
In some embodiments of the present application, lithium cobaltate is used as the active component, at least one of Na₂MoO₄, Na₂CrO₄, Na₂Ti₃O₇ or Na₃VO₄ is used as the sodium salt. The addition of the sodium salt makes the cathode material include both the lithium cobaltate phase and the sodium salt phase, and a transition region where at least the lithium cobaltate phase and the sodium salt phase are doped with each other is present at an interface of the lithium cobaltate phase and the sodium salt phase. In the transition region, at least two kinds of deintercalatable metal ions are involved in charge transfer, i.e., at the interface of the two phases, cobalt atoms and other metal atoms (at least one selected from the group of Mo, Cr, Ti and V) enter into crystals of the other phase due to the atomic diffusion to form an inter-substituted structure, which can effectively stabilize the phase interface of lithium cobaltate particles. Moreover, as the electrochemical stability and the thermal stability of the sodium salt are superior to that of the active component, the addition of the sodium salt can improve the thermal stability and the electrochemical stability of the surface of lithium cobaltate through physical or chemical bond with the active component phase at the phase interface, reduce direct contact between lithium cobaltate and an electrolyte so as to further improve the security of the battery. Furthermore, several communicated Li-ion channels are formed between these two phases, which reduces the interfacial resistance in ion migration process, optimizes the diffusion environment of Li ions and finally optimizes the cycle performance of the cathode material.
In embodiments of the present application, in order to make the cathode material have a more stable structure, the active component phase includes a hexagonal layered structure, and the sodium salt phase includes a layered structure. In this way, the cathode material has a better structural stability. Moreover, the stability of the layered sodium salt is superior to that of the hexagonal layered active component, and thus the stability of the active component can be effectively improved.
In embodiments of the present application, the sodium salt has a chemical structure of Na_aM_cO_b, wherein 0<a≤3, 0<b≤7, 0<c≤3, and M includes at least one element selected from the group of Mo, Cr, Ti and V. Therefore, the performances of the active component and the use performances of the cathode material can be improved. In embodiments of the present application, the sodium salt includes at least one selected from the group of Na₂MoO₄, Na₂CrO₄, Na₂Ti₃O₇ and Na₃VO₄, each of which has a layered structure and possesses a good structural stability, and thus can effectively improve the stability of the cathode material. As the sodium salts listed above all are intercalatable lithium compounds, and have better structural stabilities than that of lithium cobaltate, and thus can improve the stability of the cathode material better.
In embodiments of the present application, in order not to affect a specific capacity of a battery using the cathode material, a mass percent of the sodium salt is in a range of 0.1% to 10%, based on a total mass of the cathode material. In some embodiments of the present application, the mass percent of the sodium salt is in a range of 1% to 5%. Therefore, as described above, the addition of the sodium salt can effectively improve the thermal stability, electrochemical stability, expansion rate at high-temperature storage and cycle capacity retention rate of the cathode material. The sodium salt in above mass percent not only can keep the hexagonal layered structure of the main body of the cathode material, but also can effectively improve the thermal stability and electrochemical stability of the cathode material while guaranteeing a better specific capacity can be achieved using this cathode material. The performance of the cathode material is improved by fully using synergetic effects of two kinds of sodium salts with the active component, so as to further improve the use performance and service life of the cathode material. Moreover, with the increase of the addition amount of the sodium salt, the thickness expansion rate at high-temperature storage of the battery applying this cathode material will be reduced gradually, and the security of the battery will be improved. As compared with the above mass percent (0.1% to 10%), if the addition amount of the sodium salt is too low, the improvement effect is not significant, and the improvement of the electrical performance of the battery applying this cathode material is not significant either; if the addition amount of the sodium salt is excessive, the cycle performance of the cathode material will be declined, and the specific capacity of the battery applying this cathode material will be reduced either.
In embodiments of the present application, in order to avoid agglomeration of the cathode material, an average particle size of the cathode material is in a range of 0.1 µm to 20 µm. Therefore, the particle size of the cathode material is consistent with that of the active component commonly used in the battery, that is, the addition of the sodium salt does not change the particle size of the active component, thereby effectively preventing the agglomeration of the active component during the preparation of the cathode material, and avoiding the effect on the performance of cathode material.
According to embodiments of a second aspect of the present application, there is provided a method for preparing the above described cathode material. The method includes the following operations.
A mixture of a sodium salt precursor and an active component is ball-milled to obtain a cathode material precursor.
In embodiments of the present application, the sodium salt precursor is obtained by ball-milling a mixture of a sodium source, an M source and a complexing agent. The sodium source includes at least one selected from the group of Na₂CO₃, NaOH, NaNO₃, CH₃COONa and Na₃C₆H₅O₇·2H₂O, the M includes at least one element selected from the group of Mo, Cr, Ti and V, the M source includes at least one selected from the group of MoO₃, H₈MoN₂O₄, Mo(NO₃)₃·5H₂O, Cr₂O₃, CrCl₃·6H₂O, H₈CrN₂O₄, TiO₂, TiCl₄, Ti(NO₃)₄, V₂O₅, V₂O₃ and NH₄VO₃, and the complexing agent includes at least one selected from the group of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), ethylenediaminetetraacetic acid (EDTA) and glucose (C₆H₁₂O₆). These materials are cheap and widely available, and have a wide application range, from which the sodium salt precursors meeting use requirements can be prepared. With these sodium salt precursor, sodium salts, such as Na₂MoO₄, Na₂CrO₄, Na₂Ti₃O₇ or Na₃VO₄, which have stable structures and can effectively improve the structural characteristics of the active component can be effectively obtained in the subsequent operations.
In embodiments of the present application, conditions, such as time, for ball-milling the mixture of the sodium source, the M source and the complexing agent and for ball-milling the mixture of the sodium salt precursor and the active component will not be limited herein, which can be flexibly chosen by those skilled in the art according to practical demands.
In embodiments of the present application, the cathode material precursor is sintered to obtain the cathode material.
In embodiments of the present application, the sintering is performed in an oxygen or air atmosphere at a temperature of 600 °C to 1000 °C. The sintering can improve crystallinity of the sodium salt, the sodium salt obtained thereby will have a good stability, and thus the use stability and the security of the cathode material can be improved. A Lower sintering temperature (below 600 °C) is not conducive to the formation of the sodium salt, and thus the improvement effect of the cathode material is not significant; while an excessive sintering temperature (higher than 1000 °C) may cause over-sintering of the active component, which will lower the specific capacity and the cycle performance of the battery using the cathode material. However, the sintering temperature in the range of 600 °C to 1000 °C will give the cathode material a better use performance as compared with other sintering temperatures.
The method as described above has a simple, mature process and is easy to be controlled. Moreover, in the cathode material prepared with the method, the sodium salt is dispersed in the active component, the structural characteristics of the active component can be improved, synergetic effects of the sodium salt with the active component are exerted, and the particle surface stability of the cathode material is improved, so that a battery applying such a cathode material can maintain a good thermal stability and electrochemical stability, achieve a low expansion rate at high-temperature storage and a high cycle capacity retention rate (good cycle performance), keep a good specific capacity, and further improve its security and service life. Moreover, the sodium salt has a better structural stability than that of the active component, and its structural damage degree at the high voltage (usually higher than 4.3 V) is much less than that of the active component, which allows the cathode material to have a better thermal stability and electrochemical stability even at a high voltage working condition, avoiding occurrences of the phase transition and the structural collapse and the deterioration of the rate capability, thereby improving the working security and cycle performance of the cathode material.
According to embodiments of a third aspect of the present application, a cathode is provided. The cathode includes the cathode material as described hereinbefore. Therefore, the cathode has a good thermal stability and electrochemical stability, such that a battery applying such a cathode can still maintain a good thermal stability and electrochemical stability, achieve a low expansion rate at high-temperature storage and a high cycle capacity retention rate (good cycle performance), keep a good specific capacity, and further improve its security and service life, even at the high voltage.
According to embodiments of a fourth aspect of the present application, a lithium ion battery is provided. The lithium ion battery includes the cathode material or the cathode as described hereinbefore. Therefore, the battery can still maintain a good thermal stability and electrochemical stability, achieve a low expansion rate at high-temperature storage and a high cycle capacity retention rate, keep a good specific capacity, and possess a better security and a longer service life, even at the high voltage.
Certainly, it will be appreciated by those skilled in the art that, in addition to the cathode material or the cathode as described hereinbefore, the lithium ion battery has other necessary structures or components of conventional batteries, such as an anode, a separator, an electrolyte, etc. In embodiments of the present application, the anode, the separator and the electrolyte will not be specifically limited, which can be flexibly chosen by those skilled in the art according to practical demands. For example, the electrolyte may include one or more selected from the group of ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, methyl acetate and ethyl propionate. Electrolyte lithium salt includes one or more selected from the group of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, trimethyl lithium and lithium chloride. The anode includes materials which can receive or release lithium ions, such as soft carbon, hard carbon, artificial graphite, natural graphite, silicon, silicon oxide, silicon carbide complex, lithium titanate, or metals that can form alloy with lithium. The separator includes but is not limited to PE porous polymeric film.

Example

Preparation of lithium ion battery

(1) Preparation of cathode material precursor

The sodium source, the M source (M includes at least one selected from the group of Mo, Cr, Ti and V), and the complexing agent were milled in a tumbling ball mill for a period of time, then synthesized lithium cobaltate was added, proportions of these materials were controlled, the obtained mixture was ball-milled for another period of time, and then taken out of the tumbling ball mill to obtain the cathode material precursor.

(2) Preparation of cathode material

The cathode material precursor obtained in (1) was sintered in an oxygen or air atmosphere at a temperature of 600 °C to 1000 °C, and power materials produced thereby were milled to give the cathode material.

(3) Preparation of cell

The cathode material obtained in (2), acetylene black as a conductive agent, and polyvinylidene fluoride (PVDF) as an adhesive were homogeneously mixed in a weight ratio of 94:3:3 under stirring in N-methyl pyrrolidone solvent system, and then coated onto an aluminum foil, followed by drying and pressing to obtain a cathode sheet.
Artificial graphite as the active component, acetylene black as the conductive agent, styrene butadiene rubber (SBR) as the adhesive, and sodium methyl cellulose (CMC) as a thickener were homogeneously mixed in a weight ratio of 95:2:2:1 under stirring in deionized water solvent system, and then coated onto a copper foil, followed by drying and pressing to obtain an anode sheet.
The PE porous polymeric film was used as the separator.
The cathode sheet, the separator and the anode sheet were stacked in that order and wound to obtain a cell where the separator is arranged between the cathode sheet and the anode sheet to play an isolation effect. Afterwards, the cell was placed in an outer package, to which a ready formulated base electrolyte was injected, and then the outer package was packaged to obtain a lithium ion battery.

Comparative example 1:

Lithium cobaltate was directly sintered in air at 850 °C, without compounding with the sodium salt.

Comparative example 2:

Na₂CO₃ and Mo₂O₃ were milled in the tumbling ball mill for a period of time, and then lithium cobaltate was added. A proportion of Na₂MoO₄ in the resulting mixture was controlled to be 3%. The mixture was ball-milled for another period of time, and then taken out of the tumbling ball mill to obtain the cathode material.

Comparative example 3:

LiNi_0.8Co_0.1Mn_0.1O₂ material was directly sintered in air at 850 °C, without compounding with the sodium salt.

Comparative example 4:

LiNi_0.8Co_0.15Al_0.05O₂ material was directly sintered in air at 850 °C, without compounding with the sodium salt.

Example 1:

Na₂CO₃ and Cr₂O₃ were milled in the tumbling ball mill for a period of time, and then lithium cobaltate was added. A proportion of Na₂CrO₄ in the resulting mixture was controlled to be 0.1%. The mixture was ball-milled for another period of time, and then taken out of the tumbling ball mill to obtain the cathode material precursor. The cathode material precursor was sintered in air at 850 °C, and then milled to obtain the cathode material.

Example 2:

The cathode material was prepared in accordance with the same method as Example 1, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 1%.

Example 3:

The cathode material was prepared in accordance with the same method as Example 1, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 2%. The cathode material prepared thereby was tested by XRD. The test result is shown in Fig. 1.

Example 4:

The cathode material was prepared in accordance with the same method as Example 1, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 3%.

Example 5:

The cathode material was prepared in accordance with the same method as Example 1, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 4%.

Example 6:

The cathode material was prepared in accordance with the same method as Example 1, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 5%.

Example 7:

The cathode material was prepared in accordance with the same method as Example 1, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 6%.

Example 8:

The cathode material was prepared in accordance with the same method as Example 1, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 7%.

Example 9:

The cathode material was prepared in accordance with the same method as Example 1, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 8%.

Example 10:

The cathode material was prepared in accordance with the same method as Example 1, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 9%.

Example 11:

The cathode material was prepared in accordance with the same method as Example 1, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 10%.

Example 12:

Na₂CO₃ and MoO₃ were milled in the tumbling ball mill for a period of time, and then lithium cobaltate was added. A proportion of Na₂MoO₄ in the resulting mixture was controlled to be 3%. The mixture was ball-milled for another period of time, and then taken out of the tumbling ball mill to obtain the cathode material precursor. The cathode material precursor was sintered in air at 600 °C, and then milled to obtain the cathode material.

Example 13:

The cathode material was prepared in accordance with the same method as Example 12, except that the sintering temperature was 650 °C.

Example 14:

The cathode material was prepared in accordance with the same method as Example 12, except that the sintering temperature was 700 °C.

Example 15:

The cathode material was prepared in accordance with the same method as Example 12, except that the sintering temperature was 750 °C.

Example 16:

The cathode material was prepared in accordance with the same method as Example 12, except that the sintering temperature was 800 °C.

Example 17:

The cathode material was prepared in accordance with the same method as Example 12, except that the sintering temperature was 850 °C.

Example 18:

The cathode material was prepared in accordance with the same method as Example 12, except that the sintering temperature was 900 °C.

Example 19:

The cathode material was prepared in accordance with the same method as Example 12, except that the sintering temperature was 950 °C.

Example 20:

The cathode material was prepared in accordance with the same method as Example 12, except that the sintering temperature was 1000 °C.

Example 21:

The cathode material was prepared in accordance with the same method as Example 12, except that a proportion of Na₂Ti₃O₇ in the mixture was controlled to be 3%, and the sintering temperature was 600 °C.

Example 22:

The cathode material was prepared in accordance with the same method as Example 12, except that the proportion of Na₂Ti₃O₇ in the mixture was controlled to be 3%, and the sintering temperature was 850 °C.

Example 23:

The cathode material was prepared in accordance with the same method as Example 12, except that the proportion of Na₂Ti₃O₇ in the mixture was controlled to be 3%, and the sintering temperature was 1000 °C.

Example 24:

The cathode material was prepared in accordance with the same method as Example 12, except that a proportion of Na₃VO₄ in the mixture was controlled to be 3%, and the sintering temperature was 850 °C.

Example 25:

Na₂CO₃ and Cr₂O₃ were milled in the tumbling ball mill for a period of time, and then LiNi_0.8Co_0.1Mn_0.1O₂ material was added. A proportion of Na₂CrO₄ in the resulting mixture was controlled to be 3%. The mixture was ball-milled for another period of time, and then taken out of the tumbling ball mill to obtain the cathode material precursor. The cathode material precursor was sintered in air at 600 °C, and then milled to obtain the cathode material.

Example 26:

The cathode material was prepared in accordance with the same method as Example 23, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 3%, and the sintering temperature was 850 °C.

Example 27:

The cathode material was prepared in accordance with the same method as Example 23, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 3%, and the sintering temperature was 1000 °C.

Example 28:

The cathode material was prepared in accordance with the same method as Example 23, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 0.1%, and the sintering temperature was 850 °C.

Example 29:

The cathode material was prepared in accordance with the same method as Example 23, except that the proportion of Na₂CrO₄ in the mixture was controlled to be 10%, and the sintering temperature was 850 °C.

Example 30:

Na₂CO₃ and MoO₃ were milled in the tumbling ball mill for a period of time, and then LiNi_0.8Co_0.15Al_0.05O₂ material was added. A proportion of Na₂MoO₄ in the resulting mixture was controlled to be 0.1%. The mixture was ball-milled for another period of time, and then taken out of the tumbling ball mill to obtain the cathode material precursor. The cathode material precursor was sintered in air at 850 °C, and then milled to obtain the cathode material.

Example 31:

The cathode material was prepared in accordance with the same method as Example 28, except that the proportion of Na₂MoO₄ in the mixture was controlled to be 3%, and the sintering temperature was 850 °C.

Example 32:

The cathode material was prepared in accordance with the same method as Example 28, except that the proportion of Na₂MoO₄ in the mixture was controlled to be 10%, and the sintering temperature was 850 °C.
Specific capacity test: at room temperature, the battery was charged at a constant current of 0.2C (C-rate) to a voltage of 4.45 V and further charged at a constant voltage of 4.45 V until a current below 0.05C, to make the battery reach a full charge state of 4.45 V, and then discharged at a constant current of 0.2C until the voltage dropped to 3.0 V. Five batteries were tested for each of comparative examples and examples. Specific capacity data are shown in Table 1.
High temperature storage test: at room temperature, the battery was charged at a constant current of 0.5C to a voltage higher than 4.45 V, and further charged at a constant voltage of 4.45 V until a current below 0.05C, to make the battery reach a full charge state of 4.45 V. Before the storage test, a thickness of the full charged battery was tested and recorded as D0, then the full charged battery was placed in an oven at 85 °C, after storing for 24 hours, the battery was taken out of the oven and tested immediately for its thickness which was recorded as D1.
The thickness expansion rate of the battery after the high-temperature storage was calculated in accordance with the following formula: $ε = (D 1 - D 0) / D 0 \times 100 % .$
For each of comparative examples and examples, five batteries were tested, and their average thickness expansion rate was recorded, as shown in Table 1.

Cycle performance test: the lithium ion battery was charged and discharged repeatedly according to the following procedures: at 25 °C, the lithium ion battery was charged at a constant current of 0.7C (i.e., a current value at which a theoretical capacity is fully discharged within 2 h) and then charged at a constant voltage until reaching an upper limit voltage of 4.45 V, and then discharged at a constant discharging current of 0.5C to a final voltage of 3 V, and a discharge capacity of the first cycle was recorded. The charging-discharging cycle was repeated for 200 times, and a 200^th discharge capacity was recorded. The cycle capacity retention rate = (200^th discharge capacity/1^st discharge capacity) × 100%. For each of comparative examples and examples, five batteries were tested, and their average cycle capacity retention rate was recorded, as shown in Table 1.

Table 1. Experimental results of Examples and Comparative examples

	Sodium salt	Lithium salt	Sodium salt content	Average particle size of composite materials	Sintering temperature	0.2C discharge specific capacity mAh/g	Thickness expansion rate at high-temp erature storage %	Cycle capacity retention rate %
Example 1	Na₂CrO₄	LiCoO₂	0.1%	16.9µm	850 °C	172	35%	66%
Example 2	Na₂CrO₄	LiCoO₂	1%	15.6µm	850 °C	171	24%	75%
Example 3	Na₂CrO₄	LiCoO₂	2%	16.3µm	850 °C	170	19%	79%
Example 4	Na₂CrO₄	LiCoO₂	3%	15.9µm	850 °C	169	15%	83%
Example 5	Na₂CrO₄	LiCoO₂	4%	15.1µm	850 °C	166	13%	80%
Example 6	Na₂CrO₄	LiCoO₂	5%	15.7µm	850 °C	162	12%	77%
Example 7	Na₂CrO₄	LiCoO₂	6%	15.2µm	850 °C	161	12%	73%
Example 8	Na₂CrO₄	LiCoO₂	7%	16.8µm	850 °C	160	11%	72%
Example 9	Na₂CrO₄	LiCoO₂	8%	15.3µm	850 °C	159	11%	70%
Example 10	Na₂CrO₄	LiCoO₂	9%	15.6µm	850 °C	158	10%	67%
Example 11	Na₂CrO₄	LiCoO₂	10%	14.9µm	850 °C	156	9%	65%
Example 12	Na₂MoO₄	LiCoO₂	3%	15.6µm	600 °C	163	23%	65%
Example 13	Na₂MoO₄	LiCoO₂	3%	16.1µm	650 °C	163	23%	66%
Example 14	Na₂MoO₄	LiCoO₂	3%	16.3µm	700 °C	164	22%	68%
Example 15	Na₂MoO₄	LiCoO₂	3%	16.2µm	750 °C	164	21%	69%
Example 16	Na₂MoO₄	LiCoO₂	3%	16.6µm	800 °C	165	20%	71%
Example 17	Na₂MoO₄	LiCoO₂	3%	16.2µm	850 °C	167	17%	77%
Example 18	Na₂MoO₄	LiCoO₂	3%	15.9µm	900 °C	164	21%	76%
Example 19	Na₂MoO₄	LiCoO₂	3%	16.1µm	950 °C	162	25%	69%
Example 20	Na₂MoO₄	LiCoO₂	3%	16.4µm	1000 °C	159	30%	67%
Example 21	Na₂Ti₃O₇	LiCoO₂	3%	15.6µm	600 °C	163	25%	69%
Example 22	Na₂Ti₃O₇	LiCoO₂	3%	16.4µm	850 °C	164	19%	78%
Example 23	Na₂Ti₃O₇	LiCoO₂	3%	16.4µm	1000 °C	159	30%	67%
Example 24	Na₃VO₄	LiCoO₂	3%	16.7µm	850 °C	163	21%	76%
Example 25	Na₂CrO₄	LiNi_0.8Co_0.1Mn_0.1O₂	3%	15.6µm	600 °C	203	18%	80%
Example 26	Na₂CrO₄	LiNi_0.8Co_0.1Mn_0.1O₂	3%	16.1µm	850 °C	208	14%	82%
Example 27	Na₂CrO₄	LiNi_0.8Co_0.1Mn_0.1O₂	3%	16.3µm	1000 °C	202	19%	78%
Example 28	Na₂CrO₄	LiNi_0.8Co_0.1Mn_0.1O₂	0.1%	16.2µm	850 °C	206	25%	75%
Example 29	Na₂CrO₄	LiNi_0.8Co_0.1Mn_0.1O₂	10%	16.6µm	850 °C	196	16%	81%
Example 30	Na₂MoO₄	LiNi_0.8Co_0.15Al_0.05O₂	0.1%	17.9µm	850 °C	208	16%	75%
Example 31	Na₂MoO₄	LiNi_0.8Co_0.15Al_0.05O₂	3%	17.6µm	850 °C	209	9%	83%
Example 32	Na₂MoO₄	LiNi_0.8Co_0.15Al_0.05O₂	10%	17.4µm	850 °C	202	8%	78%
Comparative example 1	\	LiCoO₂	0	16.5µm	850 °C	172	36%	64%
Comparative example 2	Na₂MoO₄	LiCoO₂	3%	15.9µm	\	145	36%	57%
Comparative example 3	\	LiNi_0.8Co_0.1Mn_0.1O₂	0	17.3µm	850 °C	209	29%	62%
Comparative example 4	\	LiNi_0.8Co_0.15Al_0.05O₂	0	17.8µm	850 °C	210	25%	69%

It can be seen from the test results of comparative example 1 and examples 1-11 that, the security and cycle performance of lithium cobaltate are improved in different extents by addition of the sodium salt Na₂CrO₄, and the Na₂CrO₄ has a significant effect on the electrical property of the battery. When the mass ratio of Na₂CrO₄ to the cathode material is in a range of 0.1% to 10%, with the increase of Na₂CrO₄, the expansion rate of the battery at high-temperature storage is reduced gradually, i.e., the security of the battery is improved; however, when the mass ratio of Na₂CrO₄ is 0.1%, the improvement of the electrical property of the battery is not prominent as a result of the too little addition; when the addition amount of Na₂CrO₄ is greater than 10%, the cycle performance and discharge specific capacity of the battery are decreased markedly, the reason may be that a lithium intercalation capacity of Na₂CrO₄ also with a layered structure is lower than that of lithium cobaltate, and excessive addition of Na₂CrO₄ leads to the decrease of the discharge specific capacity of the cathode material. Therefore, moderate addition of Na₂CrO₄ will not only ensure the thermal stability and the electrochemical stability of the material itself being fully exerted, but also will not cause the discharge specific capacity of the cathode material to be lost too much, thereby making better use of synergetic effects of these two materials to improve the performances of the cathode material.
It can be seen from the test results of comparative example 1 and examples 12 to 20 that, the addition of Na₂MoO₄ has similar effects to that of Na₂CrO₄. Form a comprehensive view of the expansion rate at high-temperature storage and the cycle capacity retention rate of the battery, the expansion of the cathode material at a high temperature is reduced to a certain extent, and the cycle performance becomes better, which are due to the good stability of Na₂MoO₄ and the formation of a stable interface between Na₂MoO₄ and lithium cobaltate. Furthermore, an inter-doped structure is formed as a result of the inter-diffusion of metal atoms in the two phases, which plays a stabilizing effect on the surface of the lithium cobaltate, thereby bringing a great improvement to the stability and security of the cathode material.
From the test results of examples 12 to 20 and comparative example 2, it is demonstrated that, the sintering temperature also is a very important factor affecting the performance of the cathode material. When the sintering temperature is in the range of 600 °C to 1000 °C, the expansion rate at high-temperature storage is low, the cycle capacity retention rate is high, and the cathode material still possesses a better capacity. However, when the sintering temperature is lower, the crystallinity of the material is poor, and the performance improvement is not significant; when the sintering temperature is too high, the material will be over-sintered, also leading to the reduction of the specific capacity and the cycle performance of the material.
From the test results of examples 4, 17, 22, 24 and comparative example 1, it is demonstrated that, the addition of Na₂MoO₄, Na₂CrO₄, Na₂Ti₃O₇, or Na₃VO₄ brings improvements to the security of the cathode material in different degrees. Though different materials may have different influences on lithium cobaltate because of their own electrical conductivity and electrochemical activity, the structural stabilities of the layered sodium salts and the synergetic effects with lithium cobaltate also bring active significances to the cathode material.
As can be seen from the experimental results of comparative examples 3, 4 and examples 25 to 32, the technical solutions provided in the present application are not only suitable for lithium cobaltate, but also have similar improvement effects on the active component like lithium nickel cobalt manganite composite oxide (NCM) or lithium nickel cobalt aluminate composite oxide (NCA), thereby effectively improving the security and cycle stability of the cathode material of the battery.
The XRD diagram of the cathode material prepared according to example 3 is shown in Fig. 1, from which it can be seen that the addition of the sodium salt does not destroy the structure of lithium cobaltate, and the main structure in the cathode material is still lithium cobaltate.
Reference throughout this specification to "an embodiment," "some embodiments," "an example," "a specific example," or "some examples," means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. Thus, the appearances of the phrases such as "in some embodiments," "in one embodiment", "in an embodiment", "in another example," "in an example," "in a specific example," or "in some examples," in various places throughout this specification are not necessarily referring to the same embodiment or example of the present application. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments or examples. In addition, in the absence of contradiction, those skilled in the art can combine the different embodiments or examples described in this specification, or combine the features of different embodiments or examples.

Claims

A cathode material, comprising:
an active component; and

a sodium salt dispersed in the active component.
The cathode material according to claim 1, wherein the cathode material comprises an active component phase and a sodium salt phase, and the active component phase and the sodium salt phase are bonded via a chemical bond.
The cathode material according to claim 2, wherein a transition region where at least the active component phase and the sodium salt phase are doped with each other is present at an interface between the active component phase and the sodium salt phase.
The cathode material according to claim 2 or 3, wherein the active component phase comprises a hexagonal layered structure, and the sodium salt phase comprises a layered structure.
The cathode material according to any one of claims 1 to 4, wherein based on a total mass of the cathode material, a mass percent of the sodium salt is in a range of 0.1% to 10%, preferably in a range of 1% to 5%.
The cathode material according to any one of claims 1 to 5, wherein the sodium salt has a chemical structure of Na_aM_cO_b, wherein 0<a≤3, 0<b≤7, 0<c≤3, and M comprises at least one element selected from the group of Mo, Cr, Ti and V.
The cathode material according to claim 6, wherein the sodium salt comprises at least one selected from the group of Na₂MoO₄, Na₂CrO₄, Na₂Ti₃O₇ and Na₃VO₄.
The cathode material according to any one of claims 1 to 7, wherein the cathode material has an average particle size of 0.1 µm to 20 µm.
The cathode material according to any one of claims 1 to 8, wherein the active component comprises at least one selected from the group of lithium cobaltate, lithium nickel cobalt manganite composite oxide and lithium nickel cobalt aluminate composite oxide.
A method for preparing a cathode material, comprising:
ball-milling a mixture of a sodium salt precursor and an active component to obtain a cathode material precursor; and

sintering the cathode material precursor to obtain the cathode material.
The method according to claim 10, wherein the sodium salt precursor is obtained by ball-milling a mixture of a sodium source, an M source and a complexing agent,
wherein the sodium source comprises at least one selected from the group of Na₂CO₃, NaOH, NaNO₃, CH₃COONa and Na₃C₆H₅O₇·2H₂O, M comprises at least one element selected from the group of Mo, Cr, Ti and V, the M source comprises at least one selected from the group of MoO₃, H₈MoN₂O₄, Mo(NO₃)₃·5H₂O, Cr₂O₃, CrCl₃·6H₂O, H₈CrN₂O₄, TiO₂, TiCl₄, Ti(NO₃)₄, V₂O₅, V₂O₃ and NH₄VO₃, and the complexing agent comprises at least one selected from the group of polyvinylpyrrolidone, polyvinyl alcohol, ethylenediaminetetraacetic acid and glucose.
The method according to claim 10 or 11, wherein the sintering is performed in an oxygen or air atmosphere at a temperature of 600 °C to 1000 °C, preferably at a temperature of 850 °C to 1000 °C.
A battery cathode, comprising a cathode material according to any one of claims 1 to 9.
A lithium ion battery, comprising a cathode material according to any one of claims 1 to 9 or a battery cathode according to claim 13.
The lithium ion battery according to claim 14, further comprising a cell and an electrolyte, wherein the cell comprise the cathode, an anode and a separator, and the cathode comprises the cathode material.